CN112225919A - Geomembrane for soil remediation engineering and preparation method thereof - Google Patents
Geomembrane for soil remediation engineering and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a geomembrane for soil remediation engineering, which is characterized by comprising a high-density polyethylene film core layer, and a weather-resistant and anti-seepage layer A and a weather-resistant and anti-seepage layer B which are respectively positioned on the upper surface and the lower surface of the high-density polyethylene film core layer and are mutually independent; the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer A as well as the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer B are independently bonded by radiation grafted adhesive film layers; the weather-resistant and anti-seepage layer A and the weather-resistant and anti-seepage layer B are prepared from the same raw materials and preparation methods, and are both prepared from modified 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate. The invention also discloses a preparation method of the geomembrane for the soil remediation engineering. The geomembrane for the soil remediation engineering disclosed by the invention is good in comprehensive performance, good in weather resistance, high temperature resistance and corrosion resistance, and excellent in anti-permeability performance, mechanical property, antistatic performance and flame retardant performance.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a geomembrane for soil remediation engineering and a preparation method thereof.
Background
Soil is originally a natural accommodation place and a purification treatment place for various wastes, is one of main natural resources on which human beings live, and is also an important component of the human ecological environment. However, in recent years, with the advance of the pace of building in modern cities, the urban layout and planning land is adjusted to a great extent, and a great number of chemical fertilizer plants, pesticide plants, chemical plants and other enterprises which discharge organic wastes in large quantities are moved away from urban centers, so that a great amount of pre-industrial and commercial land which is abandoned, left unused or no longer used appears. Most of the land is contaminated seriously due to the entering of a large amount of chemicals, influences and exceeds the self-cleaning capacity of the soil, causes the composition, the structure and the function of the soil to be changed, and inhibits the activity of microorganisms; harmful substances in soil are enriched into human bodies and animal bodies through volatilization, underground water and plant adsorption and accumulation and air, water and food chains, so that the health of human and livestock is harmed, and diseases such as cancers are caused. Therefore, soil remediation is necessary before these contaminated soils are reused.
At present, the methods for soil remediation are very numerous, and mainly utilize physical, chemical and biological methods to transfer, absorb, degrade and transform pollutants in soil to reduce the concentration of the pollutants to an acceptable level, or transform toxic and harmful pollutants into harmless substances. Fundamentally, the principles of these methods for remediation of contaminated soils can include: (1) changing the existing form of the pollutants in the soil or the combination mode of the pollutants and the soil, and reducing the mobility and bioavailability of the pollutants in the environment; (2) the concentration of harmful substances in the soil is reduced. However, the existing chemical soil remediation method usually needs a soil remediation agent, the use of the soil remediation agent is easy to cause secondary pollution, and the reaction conditions cannot be controlled, so that the soil remediation efficiency is not high. The biological soil remediation method has large investment and long remediation period. The method for covering film isolation and solid sealing is one of the mainstream soil remediation technologies which are widely applied in practice and are mainly developed and popularized, and the remediation effect of the method for remedying soil depends on the performance of the covering film.
In the prior art, the common geomembranes for soil remediation engineering are high-density polyethylene membranes which have extremely low permeability coefficient and good flexibility and bring great convenience to the engineering, but the geomembranes have the problems of weak puncture resistance, heat resistance and tear resistance, and poor stability, antistatic performance and flame retardant performance in application, and the mechanical strength and the anti-corrosion capability of oily solvents are to be further improved.
The Chinese patent with application number of 200910014615.9 discloses a metallocene geomembrane which is used for seepage prevention and water prevention of railway laying, refuse landfills, tunnels, water channels, reservoirs, dams, sewage pools, ecological pools, landscape lakes, aquaculture pools and railway and highway engineering, is prepared by mixing materials through a co-extruder, and is characterized in that the metallocene geomembrane comprises the following components in percentage by weight: 64-73% of metallocene linear low-density polyethylene, 24-32% of high-density polyethylene and 0.1-3% of an auxiliary agent, wherein the auxiliary agent comprises a modification auxiliary agent and a processing auxiliary agent, and the modification auxiliary agent is an antioxidant and the processing auxiliary agent is carbon black or PPA. Good puncture resistance, good tear resistance and high tensile strength. However, the used additives have poor compatibility with polymer base materials and poor processability, and the additives are easy to bleed out during long-term use, thereby affecting the performance stability and the service life.
Therefore, the geomembrane for the soil remediation engineering, which has the advantages of good comprehensive performance, good weather resistance, high temperature resistance, good corrosion resistance, excellent anti-permeability performance, mechanical property, antistatic performance and flame retardant performance, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the soil remediation technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the geomembrane for the soil remediation engineering and the preparation method thereof, the preparation method is simple and easy to implement, the preparation efficiency and the yield are high, the geomembrane is suitable for continuous large-scale production, and the geomembrane has higher economic value, social value and ecological value; the geomembrane for soil remediation engineering prepared by the preparation method has the advantages of good comprehensive performance, good weather resistance, high temperature resistance and corrosion resistance, excellent impermeability, mechanical properties, antistatic performance and flame retardant performance.
In order to achieve the purpose, the technical scheme adopted by the invention is that the geomembrane for the soil remediation engineering is characterized by comprising a high-density polyethylene film core layer, and a weather-resistant and permeation-resistant layer A and a weather-resistant and permeation-resistant layer B which are respectively positioned on the upper surface and the lower surface of the high-density polyethylene film core layer and are mutually independent; the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer A as well as the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer B are independently bonded by radiation grafted adhesive film layers; the weather-resistant and anti-seepage layer A and the weather-resistant and anti-seepage layer B are prepared from the same raw materials and preparation methods, and are both prepared from modified 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate.
Preferably, the preparation method of the weather-resistant and permeation-resistant layer a or the weather-resistant and permeation-resistant layer B comprises the following steps:
step D1, adding 4,4 '-diaminobenzanilide and a catalyst into a high-boiling-point solvent to form a solution, dropwise adding a 15-25 mass percent N, N-dimethylformamide solution of 4,4' -diacyl chloride diphenyl ether in an ice-water bath under stirring in the atmosphere of nitrogen or inert gas within 1-2 hours, continuously stirring and reacting for 4-6 hours after dropwise adding, then precipitating in water, washing the precipitated polymer for 3-7 times by using ethanol, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain a 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate;
and D2, uniformly mixing the 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate prepared in the step D1, phosphorus pentoxide, a hyperbranched sulfonate surfactant SHBP-1, trifluoromethanesulfonic acid and phosphoric acid, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling solidification and roll calendering to obtain the weather-resistant and anti-seepage layer A or the weather-resistant and anti-seepage layer B.
Preferably, the molar ratio of the 4,4 '-diaminobenzanilide, the catalyst, the high-boiling solvent and the 4,4' -diacyl chloride diphenyl ether in the step D1 is 1 (0.8-1.2) to (6-10) to 1.
Preferably, the catalyst is at least one of triethanolamine and bis (2-hydroxyethyl) amino (trimethylol) methane.
Preferably, the high boiling point solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the inert gas is any one of helium, neon and argon.
Preferably, the mass ratio of the 4,4 '-diacyl diphenyl ether/4, 4' -diaminobenzanilide polycondensate, the phosphorus pentoxide, the hyperbranched sulfonate surfactant SHBP-1, the trifluoromethanesulfonic acid and the phosphoric acid in the step D2 is 1 (0.03-0.05):0.06:0.05: 0.02.
Preferably, the preparation method of the hyperbranched sulfonate surfactant SHBP-1 is referred to Chinese patent application publication No. CN102690641A, namely patent example 1.
Another object of the present invention is to provide a method for preparing a geomembrane for soil remediation engineering, which comprises the following steps:
step S1, performing melt extrusion, cooling solidification and roller calendering on high-density polyethylene to obtain a high-density polyethylene film core layer, then soaking the high-density polyethylene film core layer in 10-20% by mass of N, N-dimethylformamide of trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane for 1-2 hours, taking out the high-density polyethylene film core layer, placing the high-density polyethylene film core layer in a blast oven at 98-110 ℃ for drying for 4-6 hours, and performing radiation grafting at 20-30 ℃ in a nitrogen atmosphere to obtain the high-density polyethylene film core layer with the upper and lower surfaces both covered by the adhesive film layers;
and S2, overlapping the weather-resistant and permeation-resistant layer A, the high-density polyethylene film core layer with the upper and lower surfaces covered by the glue film layers and the weather-resistant and permeation-resistant layer B which are prepared in the step S1 in sequence, and pressing and hardening to obtain the geomembrane for the soil remediation engineering.
Preferably, the mass ratio of the high-density polyethylene film core layer to the trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane in the step S1 is 1 (5-10).
Preferably, the radiation source for radiation grafting is60A Co-gamma ray source, wherein the required absorbed dose is 15-50 kGy; the dose rate is 5-20 kGy/h.
Preferably, the hardening treatment in step S2 is specifically: hardening at 60-80 deg.C for 15-25 min, and then at room temperature for 7-10 hr.
Preferably, the high density polyethylene is under the designation DGDA6098, 3300F.
Preferably, the preparation method of the trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane comprises the following steps: adding the amino-terminated hyperbranched polyurethane and the trifluoro-chloro chrysanthemic acid into tetrahydrofuran, stirring and reacting for 3-5 hours at the temperature of 30-40 ℃, and then performing rotary evaporation to remove the tetrahydrofuran to obtain the trifluoro-chloro chrysanthemic acid modified amino-terminated hyperbranched polyurethane.
Preferably, the mass ratio of the amino-terminated hyperbranched polyurethane to the trifluoro-chloro chrysanthemic acid to the tetrahydrofuran is 1 (0.2-0.3) to (4-6).
Preferably, the preparation method of the amino-terminated hyperbranched polyurethane is described in chinese patent application No. 201510141212.6, example 1.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the preparation method of the geomembrane for the soil remediation engineering, provided by the invention, is simple and feasible, has high preparation efficiency and yield, is suitable for continuous large-scale production, and has higher economic value, social value and ecological value.
(2) The geomembrane for the soil restoration engineering overcomes the defects that the geomembranes commonly used for the soil restoration engineering in the prior art are high-density polyethylene films which have extremely low permeability coefficient and good flexibility and bring great convenience to the engineering, but the geomembrane has the problems of weak puncture resistance, heat resistance and tear resistance, and poor stability, antistatic performance and flame retardant performance in application, and the defects that the mechanical strength and the corrosion resistance of an oil-resistant solvent are to be further improved.
(3) The invention provides a geomembrane for soil remediation engineering, which comprises a high-density polyethylene film core layer, and a weather-resistant and permeation-resistant layer A and a weather-resistant and permeation-resistant layer B which are respectively positioned on the upper surface and the lower surface of the high-density polyethylene film core layer and are mutually independent; the structural design can better retain the advantages of the high-density polyethylene film core layer, and the influence on the anti-permeability performance and the comprehensive performance of the high-density polyethylene film core layer due to the addition of the auxiliary agent is avoided; the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer A as well as the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer B are independently bonded by radiation grafted adhesive film layers; through radiation connection, the trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane is connected to a high-density polyethylene film core layer in a chemical bond form to form a cross-linked structure, so that the comprehensive performance of the high-density polyethylene film core layer is effectively improved, and the adhesion of the polyurethane and active carboxyl groups on the polyurethane with a weather-resistant anti-seepage layer A and a weather-resistant anti-seepage layer B can be effectively improved, so that the delaminating phenomenon is effectively avoided, and the service cycle of the polyurethane is prolonged.
(4) According to the geomembrane for the soil remediation engineering, the weather-resistant and permeation-resistant layer A and the weather-resistant and permeation-resistant layer B are prepared from the same raw materials and preparation methods, and are both prepared from modified 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate; the molecular chain of the 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate contains diphenyl ether and benzanilide structures, and the synergistic effect ensures that the prepared film has better comprehensive performance and good weather resistance and impermeability; the sulfonic group on the trifluoromethanesulfonic acid reacts with the benzene ring on the molecular main chain, and the sulfone group and the fluorine-containing group are introduced, so that the weather resistance and the performance stability can be effectively improved; the antistatic property of the hyperbranched sulfonate surfactant SHBP-1 can be improved by adding the hyperbranched sulfonate surfactant SHBP-1, and the adhesive property of the hyperbranched sulfonate surfactant and the core layer can be improved by active groups on the hyperbranched sulfonate surfactant SHBP-1.
(5) According to the geomembrane for the soil remediation engineering, in order to enable the sulfonic group on the hyperbranched sulfonate surfactant SHBP-1 and the sulfonic group on the trifluoromethanesulfonic acid to have a cross-linking reaction with the benzene ring on the molecular main chain, phosphoric acid and phosphorus pentoxide are added simultaneously, and have a synergistic effect to catalyze the reaction, so that the reaction temperature can be effectively and simply generated, and the influence on the product performance caused by the gasification of the trifluoromethanesulfonic acid at an excessively high temperature is avoided.
Detailed Description
The following detailed description of preferred embodiments of the invention will be made.
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto; the preparation method of the hyperbranched sulfonate surfactant SHBP-1 is referred to Chinese invention patent example 1 with application publication number CN 102690641A; the preparation method of the amino-terminated hyperbranched polyurethane is disclosed in example 1 of the Chinese patent application No. 201510141212.6.
Example 1
Embodiment 1 provides a geomembrane for soil remediation engineering, which is characterized by comprising a high-density polyethylene film core layer, and a weather-resistant and permeation-resistant layer a and a weather-resistant and permeation-resistant layer B which are respectively located on the upper surface and the lower surface of the high-density polyethylene film core layer and are independent of each other; the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer A as well as the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer B are independently bonded by radiation grafted adhesive film layers; the weather-resistant and anti-seepage layer A and the weather-resistant and anti-seepage layer B are prepared from the same raw materials and preparation methods, and are both prepared from modified 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate.
The preparation method of the weather-resistant and permeation-resistant layer A or the weather-resistant and permeation-resistant layer B comprises the following steps:
step D1, adding 4,4 '-diaminobenzanilide and a catalyst into a high-boiling-point solvent to form a solution, then dropwise adding an N, N-dimethylformamide solution of 4,4' -diacyl chloride diphenyl ether with the mass percentage concentration of 15% into an ice-water bath while stirring in the nitrogen atmosphere, continuously stirring for reacting for 4 hours after completing dripping, then precipitating in water, washing the precipitated polymer for 3 times by using ethanol, and finally drying in a vacuum drying oven at 85 ℃ to constant weight to obtain a 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate;
and D2, uniformly mixing the 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate prepared in the step D1, phosphorus pentoxide, a hyperbranched sulfonate surfactant SHBP-1, trifluoromethanesulfonic acid and phosphoric acid, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling solidification and roll calendering to obtain the weather-resistant and anti-seepage layer A or the weather-resistant and anti-seepage layer B.
The molar ratio of the 4,4 '-diaminobenzanilide, the catalyst, the high-boiling point solvent and the 4,4' -diacyl chloride diphenyl ether in the step D1 is 1:0.8:6: 1; the catalyst is triethanolamine; the high boiling point solvent is N, N-dimethylformamide.
The mass ratio of the 4,4 '-diacyl diphenyl ether/4, 4' -diaminobenzanilide polycondensate, the phosphorus pentoxide, the hyperbranched sulfonate surfactant SHBP-1, the trifluoromethanesulfonic acid and the phosphoric acid in the step D2 is 1:0.03:0.06:0.05: 0.02.
The preparation method of the geomembrane for the soil remediation engineering is characterized by comprising the following steps of:
step S1, performing melt extrusion, cooling solidification and roller calendering on high-density polyethylene to obtain a high-density polyethylene film core layer, then soaking the high-density polyethylene film core layer in 10 mass percent of N, N-dimethylformamide of trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane for 1 hour, taking out the high-density polyethylene film core layer, placing the high-density polyethylene film core layer in a blast oven at 98 ℃ for drying for 4 hours, and performing radiation grafting at 20 ℃ in a nitrogen atmosphere to obtain the high-density polyethylene film core layer with the upper and lower surfaces both covered by adhesive film layers;
and S2, overlapping the weather-resistant and permeation-resistant layer A, the high-density polyethylene film core layer with the upper and lower surfaces covered by the glue film layers and the weather-resistant and permeation-resistant layer B which are prepared in the step S1 in sequence, and pressing and hardening to obtain the geomembrane for the soil remediation engineering.
In the step S1, the mass ratio of the high-density polyethylene film core layer to the N, N-dimethylformamide of the trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane is 1: 5.
The radiation source for the radiation grafting is60A Co-gamma ray source, wherein the required absorption dose is 15 kGy; the dose rate was 5 kGy/h.
In step S2, the hardening process specifically includes: cured at 60 ℃ for 15 minutes and then at room temperature for 7 hours.
The high density polyethylene is under the designation DGDA 6098.
The preparation method of the trichloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane comprises the following steps: adding the amino-terminated hyperbranched polyurethane and the trifluoro-chloro chrysanthemic acid into tetrahydrofuran, stirring and reacting for 3 hours at the temperature of 30 ℃, and then performing rotary evaporation to remove the tetrahydrofuran to obtain the trifluoro-chloro chrysanthemic acid modified amino-terminated hyperbranched polyurethane; the mass ratio of the amino-terminated hyperbranched polyurethane to the trifluoro-chloro chrysanthemic acid to the tetrahydrofuran is 1:0.2: 4.
Example 2
Embodiment 2 provides a geomembrane for soil remediation engineering, which is characterized by comprising a high-density polyethylene film core layer, and a weather-resistant and permeation-resistant layer a and a weather-resistant and permeation-resistant layer B which are respectively located on the upper surface and the lower surface of the high-density polyethylene film core layer and are independent of each other; the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer A as well as the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer B are independently bonded by radiation grafted adhesive film layers; the weather-resistant and anti-seepage layer A and the weather-resistant and anti-seepage layer B are prepared from the same raw materials and preparation methods, and are both prepared from modified 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate.
The preparation method of the weather-resistant and permeation-resistant layer A or the weather-resistant and permeation-resistant layer B comprises the following steps:
step D1, adding 4,4 '-diaminobenzanilide and a catalyst into a high-boiling-point solvent to form a solution, then dropwise adding a 17 mass percent N, N-dimethylformamide solution of 4,4' -diacyl chloride diphenyl ether in an ice-water bath under the condition of stirring in an inert gas atmosphere within 1.2 hours, continuously stirring for reacting for 4.5 hours after the dropwise addition is finished, then precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and finally drying in a vacuum drying oven at 87 ℃ to constant weight to obtain a 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate;
and D2, uniformly mixing the 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate prepared in the step D1, phosphorus pentoxide, a hyperbranched sulfonate surfactant SHBP-1, trifluoromethanesulfonic acid and phosphoric acid, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling solidification and roll calendering to obtain the weather-resistant and anti-seepage layer A or the weather-resistant and anti-seepage layer B.
The molar ratio of the 4,4 '-diaminobenzanilide, the catalyst, the high-boiling point solvent and the 4,4' -diacyl chloride diphenyl ether in the step D1 is 1:0.9:7: 1; the catalyst is bis (2-hydroxyethyl) amino (trihydroxymethyl) methane; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is helium.
The mass ratio of the 4,4 '-diacyl diphenyl ether/4, 4' -diaminobenzanilide polycondensate, the phosphorus pentoxide, the hyperbranched sulfonate surfactant SHBP-1, the trifluoromethanesulfonic acid and the phosphoric acid in the step D2 is 1:0.035:0.06:0.05: 0.02.
The preparation method of the geomembrane for the soil remediation engineering is characterized by comprising the following steps of:
step S1, performing melt extrusion, cooling solidification and roller calendering on high-density polyethylene to obtain a high-density polyethylene film core layer, then soaking the high-density polyethylene film core layer in 13 mass percent of N, N-dimethylformamide of trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane for 1.2 hours, taking out the high-density polyethylene film core layer, placing the high-density polyethylene film core layer in a blast oven at 102 ℃ for drying for 4.5 hours, and performing radiation grafting at 23 ℃ in a nitrogen atmosphere to obtain the high-density polyethylene film core layer with the upper and lower surfaces both covered by the film layers;
and S2, overlapping the weather-resistant and permeation-resistant layer A, the high-density polyethylene film core layer with the upper and lower surfaces covered by the glue film layers and the weather-resistant and permeation-resistant layer B which are prepared in the step S1 in sequence, and pressing and hardening to obtain the geomembrane for the soil remediation engineering.
In the step S1, the mass ratio of the high-density polyethylene film core layer to the N, N-dimethylformamide of the trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane is 1: 6.
The radiation source for the radiation grafting is60Co-gamma ray source, the required absorbed dose is 25kGy; the dose rate was 10 kGy/h.
In step S2, the hardening process specifically includes: cured at 65 ℃ for 17 minutes and then at room temperature for 8 hours.
The high density polyethylene has a grade of 3300F.
The preparation method of the trichloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane comprises the following steps: adding the amino-terminated hyperbranched polyurethane and the trifluoro-chloro chrysanthemic acid into tetrahydrofuran, stirring and reacting for 3.5 hours at 33 ℃, and then performing rotary evaporation to remove the tetrahydrofuran to obtain the trifluoro-chloro chrysanthemic acid modified amino-terminated hyperbranched polyurethane; the mass ratio of the amino-terminated hyperbranched polyurethane to the trifluoro-chloro chrysanthemic acid to the tetrahydrofuran is 1:0.23: 4.5.
Example 3
Embodiment 3 provides a geomembrane for soil remediation engineering, which is characterized by comprising a high-density polyethylene film core layer, and a weather-resistant and permeation-resistant layer a and a weather-resistant and permeation-resistant layer B which are respectively located on the upper surface and the lower surface of the high-density polyethylene film core layer and are independent of each other; the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer A as well as the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer B are independently bonded by radiation grafted adhesive film layers; the weather-resistant and anti-seepage layer A and the weather-resistant and anti-seepage layer B are prepared from the same raw materials and preparation methods, and are both prepared from modified 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate.
The preparation method of the weather-resistant and permeation-resistant layer A or the weather-resistant and permeation-resistant layer B comprises the following steps:
step D1, adding 4,4 '-diaminobenzanilide and a catalyst into a high-boiling-point solvent to form a solution, then dropwise adding an N, N-dimethylformamide solution of 4,4' -diacyl chloride diphenyl ether with the mass percentage concentration of 20% in an ice-water bath under the atmosphere of inert gas while stirring, continuously stirring for reacting for 5 hours after completing dripping, then precipitating in water, washing the precipitated polymer for 5 times by using ethanol, and finally drying in a vacuum drying oven at 90 ℃ to constant weight to obtain a 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate;
and D2, uniformly mixing the 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate prepared in the step D1, phosphorus pentoxide, a hyperbranched sulfonate surfactant SHBP-1, trifluoromethanesulfonic acid and phosphoric acid, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling solidification and roll calendering to obtain the weather-resistant and anti-seepage layer A or the weather-resistant and anti-seepage layer B.
In the step D1, the molar ratio of the 4,4 '-diaminobenzanilide, the catalyst, the high-boiling-point solvent and the 4,4' -diacyl chloride diphenyl ether is 1:1:8: 1; the catalyst is triethanolamine; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is neon.
The mass ratio of the 4,4 '-diacyl diphenyl ether/4, 4' -diaminobenzanilide polycondensate, the phosphorus pentoxide, the hyperbranched sulfonate surfactant SHBP-1, the trifluoromethanesulfonic acid and the phosphoric acid in the step D2 is 1:0.04:0.06:0.05: 0.02.
The preparation method of the geomembrane for the soil remediation engineering is characterized by comprising the following steps of:
step S1, performing melt extrusion, cooling solidification and roller calendering on high-density polyethylene to obtain a high-density polyethylene film core layer, then soaking the high-density polyethylene film core layer in N, N-dimethylformamide of trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane with the mass percentage concentration of 15% for 1.5 hours, taking out the high-density polyethylene film core layer, placing the high-density polyethylene film core layer in a blast oven with the temperature of 105 ℃ for drying for 5 hours, and performing radiation grafting at the temperature of 25 ℃ in a nitrogen atmosphere to obtain the high-density polyethylene film core layer with the upper and lower surfaces both covered by the film layers;
and S2, overlapping the weather-resistant and permeation-resistant layer A, the high-density polyethylene film core layer with the upper and lower surfaces covered by the glue film layers and the weather-resistant and permeation-resistant layer B which are prepared in the step S1 in sequence, and pressing and hardening to obtain the geomembrane for the soil remediation engineering.
In the step S1, the mass ratio of the high-density polyethylene film core layer to the N, N-dimethylformamide of the trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane is 1: 7.5.
The radiation source for the radiation grafting is60A Co-gamma ray source, wherein the required absorption dose is 40 kGy; the dose rate was 15 kGy/h.
In step S2, the hardening process specifically includes: cured at 70 ℃ for 20 minutes and then at room temperature for 8.5 hours.
The high density polyethylene is under the designation DGDA 6098.
The preparation method of the trichloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane comprises the following steps: adding the amino-terminated hyperbranched polyurethane and the trifluoro-chloro chrysanthemic acid into tetrahydrofuran, stirring and reacting for 4 hours at 35 ℃, and then performing rotary evaporation to remove the tetrahydrofuran to obtain the trifluoro-chloro chrysanthemic acid modified amino-terminated hyperbranched polyurethane; the mass ratio of the amino-terminated hyperbranched polyurethane to the trifluoro-chloro chrysanthemic acid to the tetrahydrofuran is 1:0.25: 5.
Example 4
Embodiment 4 provides a geomembrane for soil remediation engineering, which is characterized by comprising a high-density polyethylene film core layer, and a weather-resistant and permeation-resistant layer a and a weather-resistant and permeation-resistant layer B which are respectively located on the upper surface and the lower surface of the high-density polyethylene film core layer and are independent of each other; the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer A as well as the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer B are independently bonded by radiation grafted adhesive film layers; the weather-resistant and anti-seepage layer A and the weather-resistant and anti-seepage layer B are prepared from the same raw materials and preparation methods, and are both prepared from modified 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate.
The preparation method of the weather-resistant and permeation-resistant layer A or the weather-resistant and permeation-resistant layer B comprises the following steps:
step D1, adding 4,4 '-diaminobenzanilide and a catalyst into a high-boiling-point solvent to form a solution, then dropwise adding an N, N-dimethylformamide solution of 4,4' -diacyl chloride diphenyl ether with the mass percentage concentration of 23% in an ice-water bath under the atmosphere of inert gas while stirring, continuously stirring for reacting for 5.5 hours after completing dripping, then precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally drying in a vacuum drying oven at 93 ℃ to constant weight to obtain a 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate;
and D2, uniformly mixing the 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate prepared in the step D1, phosphorus pentoxide, a hyperbranched sulfonate surfactant SHBP-1, trifluoromethanesulfonic acid and phosphoric acid, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling solidification and roll calendering to obtain the weather-resistant and anti-seepage layer A or the weather-resistant and anti-seepage layer B.
The molar ratio of the 4,4 '-diaminobenzanilide, the catalyst, the high-boiling point solvent and the 4,4' -diacyl chloride diphenyl ether in the step D1 is 1:1.1:9.5: 1; the catalyst is formed by mixing triethanolamine and bis (2-hydroxyethyl) amino (trihydroxymethyl) methane according to the mass ratio of 3: 5; the high-boiling-point solvent is formed by mixing N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:3: 2; the inert gas is argon.
In the step D2, the mass ratio of the 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate, the phosphorus pentoxide, the hyperbranched sulfonate surfactant SHBP-1, the trifluoromethanesulfonic acid and the phosphoric acid is 1:0.045:0.06:0.05: 0.02.
The preparation method of the geomembrane for the soil remediation engineering is characterized by comprising the following steps of:
step S1, performing melt extrusion, cooling solidification and roller calendering on high-density polyethylene to obtain a high-density polyethylene film core layer, then soaking the high-density polyethylene film core layer in 19 mass percent of N, N-dimethylformamide of trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane for 1.8 hours, taking out the high-density polyethylene film core layer, placing the high-density polyethylene film core layer in a blast oven at 108 ℃ for drying for 5.5 hours, and performing radiation grafting at 29 ℃ in a nitrogen atmosphere to obtain the high-density polyethylene film core layer with the upper and lower surfaces both covered by film layers;
and S2, overlapping the weather-resistant and permeation-resistant layer A, the high-density polyethylene film core layer with the upper and lower surfaces covered by the glue film layers and the weather-resistant and permeation-resistant layer B which are prepared in the step S1 in sequence, and pressing and hardening to obtain the geomembrane for the soil remediation engineering.
In the step S1, the mass ratio of the high-density polyethylene film core layer to the N, N-dimethylformamide of the trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane is 1:9.
The radiation source for the radiation grafting is60A Co-gamma ray source, wherein the required absorption dose is 45 kGy;the dose rate was 18 kGy/h.
In step S2, the hardening process specifically includes: cured at 75 ℃ for 23 minutes and then at room temperature for 9.5 hours.
The high density polyethylene is under the designation DGDA 6098.
The preparation method of the trichloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane comprises the following steps: adding the amino-terminated hyperbranched polyurethane and the trifluoro-chloro chrysanthemic acid into tetrahydrofuran, stirring and reacting for 4.5 hours at 38 ℃, and then performing rotary evaporation to remove the tetrahydrofuran to obtain the trifluoro-chloro chrysanthemic acid modified amino-terminated hyperbranched polyurethane; the mass ratio of the amino-terminated hyperbranched polyurethane to the trifluoro-chloro chrysanthemic acid to the tetrahydrofuran is 1:0.28: 5.5.
Example 5
Embodiment 5 provides a geomembrane for soil remediation engineering, which is characterized by comprising a high-density polyethylene film core layer, and a weather-resistant and permeation-resistant layer a and a weather-resistant and permeation-resistant layer B which are respectively located on the upper surface and the lower surface of the high-density polyethylene film core layer and are independent of each other; the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer A as well as the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer B are independently bonded by radiation grafted adhesive film layers; the weather-resistant and anti-seepage layer A and the weather-resistant and anti-seepage layer B are prepared from the same raw materials and preparation methods, and are both prepared from modified 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate.
The preparation method of the weather-resistant and permeation-resistant layer A or the weather-resistant and permeation-resistant layer B comprises the following steps:
step D1, adding 4,4 '-diaminobenzanilide and a catalyst into a high-boiling-point solvent to form a solution, then dropwise adding an N, N-dimethylformamide solution of 4,4' -diacyl chloride diphenyl ether with the mass percentage concentration of 25% into an ice-water bath while stirring in the atmosphere of nitrogen, continuously stirring and reacting for 6 hours after dropwise adding, then precipitating in water, washing the precipitated polymer for 7 times by using ethanol, and finally drying in a vacuum drying oven at 95 ℃ to constant weight to obtain a 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate;
and D2, uniformly mixing the 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate prepared in the step D1, phosphorus pentoxide, a hyperbranched sulfonate surfactant SHBP-1, trifluoromethanesulfonic acid and phosphoric acid, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling solidification and roll calendering to obtain the weather-resistant and anti-seepage layer A or the weather-resistant and anti-seepage layer B.
In the step D1, the molar ratio of the 4,4 '-diaminobenzanilide, the catalyst, the high-boiling-point solvent and the 4,4' -diacyl chloride diphenyl ether is 1:1.2:10: 1; the catalyst is bis (2-hydroxyethyl) amino (trihydroxymethyl) methane; the high boiling point solvent is N, N-dimethylformamide.
The mass ratio of the 4,4 '-diacyl diphenyl ether/4, 4' -diaminobenzanilide polycondensate, the phosphorus pentoxide, the hyperbranched sulfonate surfactant SHBP-1, the trifluoromethanesulfonic acid and the phosphoric acid in the step D2 is 1:0.05:0.06:0.05: 0.02.
The preparation method of the geomembrane for the soil remediation engineering is characterized by comprising the following steps of:
step S1, performing melt extrusion, cooling solidification and roller calendering on high-density polyethylene to obtain a high-density polyethylene film core layer, then soaking the high-density polyethylene film core layer in N, N-dimethylformamide of 20 mass percent of trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane, taking out the high-density polyethylene film core layer, placing the high-density polyethylene film core layer in a forced air oven at 110 ℃ for drying for 6 hours, and performing radiation grafting at 30 ℃ in a nitrogen atmosphere to obtain the high-density polyethylene film core layer with the upper and lower surfaces both covered by adhesive film layers;
and S2, overlapping the weather-resistant and permeation-resistant layer A, the high-density polyethylene film core layer with the upper and lower surfaces covered by the glue film layers and the weather-resistant and permeation-resistant layer B which are prepared in the step S1 in sequence, and pressing and hardening to obtain the geomembrane for the soil remediation engineering.
In the step S1, the mass ratio of the high-density polyethylene film core layer to the N, N-dimethylformamide of the trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane is 1: 10.
The radiation source for the radiation grafting is60A Co-gamma ray source, wherein the required absorption dose is 50 kGy; the dose rate was 20 kGy/h.
In step S2, the hardening process specifically includes: cured at 80 ℃ for 25 minutes and then at room temperature for 10 hours.
The high density polyethylene has a grade of 3300F.
The preparation method of the trichloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane comprises the following steps: adding the amino-terminated hyperbranched polyurethane and the trifluoro-chloro chrysanthemic acid into tetrahydrofuran, stirring and reacting for 5 hours at 40 ℃, and then performing rotary evaporation to remove the tetrahydrofuran to obtain the trifluoro-chloro chrysanthemic acid modified amino-terminated hyperbranched polyurethane; the mass ratio of the amino-terminated hyperbranched polyurethane to the trifluoro-chloro chrysanthemic acid to the tetrahydrofuran is 1:0.3: 6.
Comparative example 1
Comparative example 1 provides a geomembrane for soil reclamation works, which has a formulation and a preparation method substantially the same as those of example 1 except that 4,4 '-diacyl diphenyl ether/4, 4' -diaminobenzanilide polycondensate is used instead of the modified 4,4 '-diacyl diphenyl ether/4, 4' -diaminobenzanilide polycondensate.
Comparative example 2
Comparative example 2 provides a geomembrane for soil remediation engineering, the formulation and preparation method of which are substantially the same as in example 1, except that trichlorochrysanthemic acid is used instead of trichlorochrysanthemic acid-modified amino terminated hyperbranched polyurethane.
Comparative example 3
Comparative example 3 provides a geomembrane for soil remediation engineering, which is a commercially available high density polyethylene film.
The geomembranes for soil reclamation projects described in examples 1 to 5 and comparative examples 1 to 3 were subjected to performance tests, and the test results and test methods are shown in table 1.
TABLE 1
| Detecting items | Tensile yield strength, MPa | Limit oxygen index% | Water vapor permeability coefficient, g.cm/(cm)2.s.Pa) | Resistance to stress cracking, h | Puncture resistance strength, N |
| Detection standard | GB/T17643-2011 | GB/T2406-1993 | GB/T1037-1988 | GB/T17643-2011 | GB/T17632 |
| Example 1 | 39.5 | 36 | 2.3×10-22 | 530 | 670 |
| Example 2 | 39.9 | 37 | 1.9×10-22 | 534 | 673 |
| Example 3 | 40.2 | 37 | 1.4×10-22 | 537 | 675 |
| Example 4 | 40.4 | 38 | 0.9×10-22 | 541 | 678 |
| Example 5 | 40.7 | 38 | 0.7×10-22 | 545 | 680 |
| Comparative example 1 | 30.4 | 34 | 1.5×10-16 | 506 | 588 |
| Comparative example 2 | 33.8 | 33 | 1.8×10-19 | 512 | 595 |
| Comparative example 3 | 30.8 | 26 | 2.0×10-14 | 385 | 494 |
As can be seen from table 1, the geomembrane for soil remediation engineering disclosed in the examples of the present invention has more excellent mechanical properties, flame retardancy, and impermeability than the comparative examples, which are the result of the synergistic effect of the respective films and the respective raw material formulations.
The above-mentioned embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (9)
1. The geomembrane for the soil remediation engineering is characterized by comprising a high-density polyethylene film core layer, and a weather-resistant and anti-seepage layer A and a weather-resistant and anti-seepage layer B which are respectively positioned on the upper surface and the lower surface of the high-density polyethylene film core layer and are mutually independent; the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer A as well as the high-density polyethylene film core layer and the weather-resistant and anti-permeation layer B are independently bonded by radiation grafted adhesive film layers; the weather-resistant and anti-seepage layer A and the weather-resistant and anti-seepage layer B are prepared from the same raw materials and preparation methods, and are both prepared from modified 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate.
2. The geomembrane for soil remediation engineering according to claim 1, wherein the preparation method of the weather-resistant and permeation-resistant layer A or the weather-resistant and permeation-resistant layer B comprises the following steps:
step D1, adding 4,4 '-diaminobenzanilide and a catalyst into a high-boiling-point solvent to form a solution, dropwise adding a 15-25 mass percent N, N-dimethylformamide solution of 4,4' -diacyl chloride diphenyl ether in an ice-water bath under stirring in the atmosphere of nitrogen or inert gas within 1-2 hours, continuously stirring and reacting for 4-6 hours after dropwise adding, then precipitating in water, washing the precipitated polymer for 3-7 times by using ethanol, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain a 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate;
and D2, uniformly mixing the 4,4 '-diacyl chloride diphenyl ether/4, 4' -diaminobenzanilide polycondensate prepared in the step D1, phosphorus pentoxide, a hyperbranched sulfonate surfactant SHBP-1, trifluoromethanesulfonic acid and phosphoric acid, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling solidification and roll calendering to obtain the weather-resistant and anti-seepage layer A or the weather-resistant and anti-seepage layer B.
3. The geomembrane for soil remediation engineering according to claim 2, wherein the molar ratio of the 4,4 '-diaminobenzanilide, the catalyst, the high boiling point solvent and the 4,4' -diacyl diphenyl ether in the step D1 is 1 (0.8-1.2) to 1 (6-10).
4. The geomembrane for soil remediation engineering according to claim 2, wherein said catalyst is at least one of triethanolamine, bis (2-hydroxyethyl) amino (trimethylol) methane; the high boiling point solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of helium, neon and argon.
5. The geomembrane for soil remediation engineering according to claim 2, wherein the mass ratio of the 4,4 '-diacyl diphenyl ether/4, 4' -diaminobenzanilide polycondensate, the phosphorus pentoxide, the hyperbranched sulfonate surfactant SHBP-1, the trifluoromethanesulfonic acid and the phosphoric acid in step D2 is 1 (0.03-0.05):0.06:0.05: 0.02.
6. The geomembrane for soil reclamation engineering as recited in any one of claims 1 to 5, wherein said method for preparing a geomembrane for soil reclamation engineering comprises the steps of:
step S1, performing melt extrusion, cooling solidification and roller calendering on high-density polyethylene to obtain a high-density polyethylene film core layer, then soaking the high-density polyethylene film core layer in 10-20% by mass of N, N-dimethylformamide of trifluoro-chloro-chrysanthemic acid modified amino-terminated hyperbranched polyurethane for 1-2 hours, taking out the high-density polyethylene film core layer, placing the high-density polyethylene film core layer in a blast oven at 98-110 ℃ for drying for 4-6 hours, and performing radiation grafting at 20-30 ℃ in a nitrogen atmosphere to obtain the high-density polyethylene film core layer with the upper and lower surfaces both covered by the adhesive film layers;
and S2, overlapping the weather-resistant and permeation-resistant layer A, the high-density polyethylene film core layer with the upper and lower surfaces covered by the glue film layers and the weather-resistant and permeation-resistant layer B which are prepared in the step S1 in sequence, and pressing and hardening to obtain the geomembrane for the soil remediation engineering.
7. The geomembrane for soil remediation engineering according to claim 6, wherein the mass ratio of the high-density polyethylene film core layer to the N, N-dimethylformamide of the trifluoro-chloroauric acid modified amino-terminated hyperbranched polyurethane in the step S1 is 1 (5-10); the radiation source for the radiation grafting is60A Co-gamma ray source, wherein the required absorbed dose is 15-50 kGy; the dosage rate is 5-20 kGy/h; in step S2, the hardening process specifically includes: hardening for 15-25 minutes at 60-80 ℃, and then hardening for 7-10 hours at room temperature; the high density polyethylene is under the trade mark DGDA6098, 3300F.
8. The geomembrane for soil remediation engineering according to claim 6, wherein the preparation method of the trichlorochloranthus-modified amino-terminated hyperbranched polyurethane comprises the following steps: adding the amino-terminated hyperbranched polyurethane and the trifluoro-chloro chrysanthemic acid into tetrahydrofuran, stirring and reacting for 3-5 hours at the temperature of 30-40 ℃, and then performing rotary evaporation to remove the tetrahydrofuran to obtain the trifluoro-chloro chrysanthemic acid modified amino-terminated hyperbranched polyurethane.
9. The geomembrane for soil remediation engineering according to claim 8, wherein the mass ratio of the amino-terminated hyperbranched polyurethane to the trifluoro-chloro chrysanthemic acid to the tetrahydrofuran is 1 (0.2-0.3) to (4-6).
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